Process for the preparation of strongly lathering and purifying agents, shampoos, and the like



Patented Oct. 16, 195.1

PROCESS FOR THE PREPARATION OF STRONGLY LATHERING AND PURI- FYING AGENTS, SHAMPOOS, AND

THE LIKE 'Petrus 'Bernardus Hubcrtus Maria Dobbelmann and Johannes van Loon, Nimeguen, Netherlands, assignors to Dobbelman N. V., Nimeguen,

Netherlands N Drawing. Application October 30, 1947;Serial No. 783,208. In the Netherlands November 1,

1-0Claims. (Cl. 252-121) 'This invention relates to the preparation of detergents having a great lathering capacity and agreat detergent action, are resistant to hard and salt waterandpreferablyreactneutrally but are also active in weakly acid and alkaline medium.

Itis known that ester salts (e. g.

SO; Na

in which R is a hydrocarbon radical or group having a secondary carbon atom, as for example compounds of the formula in which R1 and R2 are aliphatic hydrocarbon radicals and the group R1-C-Rz contains from to 18 carbon atoms) have the following properties.

1. Their solutions strongly reduce the surface tension, lather strongly and therefore have a certain detergent action.

2. They do not give rise to the formation of insoluble calcium and magnesium salts when using hard water.

3. In solution they have a neutral action.

'4. They can be acidified without objection, without their lathering or detergent action being prejudicially influenced.

5. Their detergent action does not decrease in salt-containing water, such as sea water.

They have thus certain favourable properties which soap or soap solutions do not have. Soaps namely give rise to insoluble calcium and magnesium soaps in'hard water, which unnecessarily increase the soap consumption and causes undesired salt precipitation on the material to be washed. Also soaps in aqueous solution owing to hydrolysis give a more or less alkaline reaction which may have an unfavourable influence on thematerial to'be washed. In acid medium soaps decompose with the formation of fatty acid which decreases or even nullifies the washing and purifying action of the soap whereas most kinds of soap in salt-containing water, such as sea water, sho'wn'o or practically no washing action. However, when using ester salt solutions for washing purposes the following drawbacks occur.

1. The lather formed is abundant but has coarse bubles and is little stable, so that no-fat broth as is .usual with soap sol'utions,=isobtained which broth isappreciatedin practice.

2. The detergent action is not yet perfect if this is compared With-that of other products.

The purpose of the invention is toimprove these properties which are present in insuflicient quantity, whereas the good properties, such as the resistance to hard water, to acids and if desired, the neutral reaction in aqueous solution,-

etc., are maintained. Thesmell, colour, 'solubility, etc. are not unfavourable influenced either.

According to the invention these objects are attained by mixing ester salts with resinous products and particularly neutral or acid salts of resinous acids. This was not'at all -to "be expected, because the salts of the resinous acids behave in many respects as saltsof high molecular fatty acids.

Whereas however, the latter do not 'or practically not dissolve in the ester salt-solutions this appears-to be the case with salts'ofresinous acids and even to rather high concentrations as well of these salts as of the ester salts. inous acids and the resin per se dissolverather well in the ester salt solution. In both cases clear, more or less lightly coloured solutions are obtained showing improved qualities with regard to the pure ester salt solution. It is very surprising that also-resin and resinous acids, which per se are not soluble in water, dissolved-inc. g. a 20% ester salt solution donot precipitate when the solution is diluted. From this the conclusion must be drawn that in this case no-ordinary solution ofthese two-substituents is-obtained but that a soluble compound is formed, be it-probably a little stable one.

Afurther investigation of these solutions indicated that resinous acids do not decrease the lathering capacity of ester salt solutions, that salts of resinous acids reduce same very little, whereas fatty acids and fatty acid salts do same in a strongdegree. Consequently there is a characteristic difference in this-case between the resinous acids and also their salts on the one hand i and the higher fatty acids and also their salts on the other hand, which undoubtedly is also caused by the fact that evidently the resinous acids, and also'their salts enter into combination with the ester salts.

Moreover the addition of'resinous salts'to ester salts gives rise to a considerably improved lather, as Well with regard to the quantity as to the quality thereof. In contradistinction with an ester salt solution that one which contains also resinous acid salts gives a thicklather with fine" Also the resbubbles of high stability. The product according to the invention consequently gives a desired abundantly lathering fat broth, the lather of which does not disappear quickly.

It also appears that the detergent action has increased and surpasses by far that of soap solutions with a similar content of active substance.

It is already known that the salts of resinous acids in hard water neither give insoluble calcium and magnesium soaps, nor are precipitated by salt solutions in case that the concentrations thereof are of such an order of greatness as occurs in nature or even when these concentrations are greater. The requirement that the improved product must be resistant to hard water and to sea water is therefore also complied with.

The quantity of resin and or resinate added is rather large, viz. 15-50% of the quantity of ester salt whereas preferably 30-40% are added.

Whereas ester salt solutions are completely neutral, consequently have a pH value 7 it could be expected that this is no more the case in the presence of resinous acid salts as these hydrolyse in a certain degree in aqueous solution. It appears, however, that same does not give rise to difliculties in the present case.

The resin and the resinous acid as well as the resinous salts dissolve in the ester salt solution without the lathering capacity etc. prejudicially influencing in any degree the saponification of the resin, and also the neutralization of the resinous acids which can be controlled such that this takes place incompletely and consequently a certain excess of resinous acids is present. On dilution with water it was surprisingly established that although a certain hydrolysis of the resinous salts takes place the pH value does not exceed '7.

It also appears, probably because the resinous acid converts with the ester salts to a compound, that the pH changes only very little on dilution because of a certain buffering action and that same adjusts itself automatically at a value of approximately 6-7.

The ester salts enriched according to the inlution) are added in coarsely granulated condition.

The addition can also take place at a lower temperature but the conversion then takes place less smoothly whereas a higher temperature gives rise to a too strong lather formation. After all resin or the like having been dissolved it is allowed to cool and the pH value is controlled in such a manner by the addition of alkali or acid that same does not become higher than 7 with the necessary dilution. At the same time other desired constituents such as glycerol, perfume, colouring agent or the detergent action promoting salts, such as phosphates, etc. can be added.

Example II When using solid ester salts or ester salts separated from solution by lye washing agents, sham- Docs and the like can be prepared in dry condition.

One can then proceed in the following manner.

Solid ester salts can be kneaded with lye and the necessary quantity of molten resin or the like and left alone at room temperature or somewhat elevated temperature for some time in order to obtain a complete conversion. The rather pastelike water containing mass obtained can be dried by kneading with anhydrous pyrophosphate and by making of an excess of pyrophosphate be brought in such a form that the product can be pulverized and sieved. The pyrophosphate considerably contributes to the detergent action and cannot be regarded as an indifferent filler.

When ester salts separated by lye from a solution are started with, the lye remaining in these salts can be neutralized by kneading with the desired quantity of molten resin and if still an excess of lye should be present the non-combined, lye can be neutralized with acid pyrophosphate (anhydrous) whereupon by the addition of neutral pyrophosphate (anhydrous) the mass is converted into a dry product that is pulverized and vention with resinous salts consequently have not sievedonly maintained the original favourable properties but also obtained new ones making them more and better suitable as a detergent, shampoo, etc. than when no resin or resinous salts have been added.

As resin for the preparation of the resinous salts the ordinary colophony can be applied. Without objection also e. g. improved products prepared from colophony can be used, such as hydrogenated, polymerized, dehydrogenized colophony, etc. without principal changes with regard to the above explanations resulting therefrom. The same is valid for resins of other origin but with similar properties or their impoved forms.

The working up of resinous salts can take place as well with ester salts as such as in solution.

The invention is further elucidated by the following examples.

Example I When making a solution one can proceed as follows: An ester salt solution with a content of 20% of active substance is heated to 80-90 C. 70

with the quantity of alkali or alkaline reaction substances necessary for the neutralization or saponification of the resin, whereupon under strong agitation 30% of resin or the like (calcu- The addition of colouring matter, perfume, etc.

can in this method take place'in the kneading apparatus.

Also these solid products have the above mentioned desired properties.

Of course in preparing the products one is not restricted to the above indicated concentrations On the contrary according place can be altered. Also other desired products can be taken up. It is to be understood that the term rosin product used in the claims 0 is intended to include resin or the resin products referred to in the specification, rosins, derivatives of resins and their water-soluble salts, unless otherwise limited.

We claim:

mixing a solution of a water soluble salt of a sulfate ester containing a hydrocarbon group having a secondary carbon atom With strong lye and thereby separating out the salt of the sulfate ester, and mixing therewith and saponifying a molten unsaponified rosin product, suificient lye being used and present in the sulfate ester salt lated on the active substance of the ester salt soto saponify and. neutralize the rosin product, the

rosin product comprising between 15% and 50% of the quantity of the sulfate ester salt.

2. A process as defined by claim 1 in which a paste-like product is obtained, and drying such product.

3. A process as defined by claim 1 in which a paste-like product is obtained, drying the resulting paste-like product and mixing therewith an anhydrous alkali metal pyrophosphate.

4. A process as defined by claim 1 characterized in that the product has a pH of approximatel 6 to 7.

5. A process for the preparation of strongly lathering and purifying washing agents adapted for use in hard water and sea water, comprising mixing in dry condition a water soluble salt of a sulfate ester containing a hydrocarbon group having a secondary carbon atom, an unsaponified rosin product, and sufficient alkali to efiect neutralization and saponifica-tion of the rosin product, and kneading the mixture to eifect saponification of the rosin product, said rosin product being present in the mixture to the extent of from 15% to 50% of the quantity of the sulfate ester salt therein.

6. A process as defined by claim 5 characterized in that a paste-like mixture is obtained, and drying the paste-like mixture.

7. A process as defined by claim 5 characterized in that a paste-like mixture is obtained, drying the paste-like mixture, and mixing with the dry material an anhydrous alkali metal pyrophosphate.

8. A process as defined by claim 5 characterized 6 in that the mixture has a pH of approximately 6 to 7.

9. A strongly lathering and purifying washing agent for use in hard water and sea, water, comprising a composition containing a water soluble salt of a sulfate ester containing a hydrocarbon group having a secondary carbon atom and a water soluble salt of a rosin product, the salt of the rosin product comprising between 15% and 50% of the salt of the sulfate ester.

10. A washing agent as claimed in claim 9 characterized in that the composition has a pH value of approximately 6 to 7.

PETRUS BERNARDUS HUBERTUS MARIA DOBBELMANN. J OI-IANNES VAN LOON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,040,673 Robinson May 12, 1936 2,088,020 Wickert July 27, 1937 2,390,295 Flett Dec. 4, 1945 2,414,452 Cunder Jan. 21, 19 7 FOREIGN PATENTS Number Country Date 379,534 Great Britain Sept. 1, 1932 584,500 Great Britain Jan. 16, 1947 109,842 Australia Feb. 29, 1940 

1. A PROCESS FOR THE PREPARATION OF STRONGLY LATHERING AND PURIFYING WASHING AGENTS ADAPTED FOR USE IN HARD WATER AND SEA WATER, COMPRISING MIXING A SOLUTION OF A WATER SOLUBLE SALT OF A SULFATE ESTER CONTAINING A HYDROCARBON GROUP HAVING A SECONDARY CARBON ATOM WITH STRONG LYE AND THEREBY SEPARATING OUT THE SALT OF THE SULFATE ESTER, AND MIXING THEREWITH AND SAPONIFYING A MOLTEN UNSAPONIFIED ROSIN PRODUCT, SUFFICIENT LYE BEING USED AND PRESENT IN THE SULFATE ESTER SALT TO SAPONIFY AND NEUTRALIZE THE ROSIN PRODUCT, THE ROSIN PRODUCT COMPRISING BETWEEN 15% AND 50% OF THE QUANTITY OF THE SULFATE ESTER SALT. 